The Preparation of Ammonolysis and Aminolysis Products of Bis(cyclopentadienyl)titanium Dichloride

Baye, Lawrence J.

doi:10.1080/00945717208069577

Cited by 14 publications

(2 citation statements)

References 5 publications

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“…Therefore, they should react with Lewis bases like tertiary amines to form adducts of the type Cp 2 MCl 2 ←NR 3 . Such reactions are rarely discussed in the literature and are controversial …”

Section: Resultsmentioning

confidence: 99%

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

et al. 1996

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Dehydrocupling of phenylsilaneMixed bent sandwich titanium(IV) complexes containing the donor-substituted [2-(diisopropylamino)ethyl]cyclopentadienyl (C5H4CH2CH2NiPr2 = CpN) ligand are described. The highly moisture-sensitive metallocene dichloride ( C5H4CH2CH2NNiFV2)(C5H4SiMe3)TiC12 (1) was synthesized by reaction of CpNLi with CpSTiCl3 (Cps = C5hSiMe3). Complex 1 reacts with one equivalent of HCl with protonation of the amino group to give the air-and water-stable metallocene dichloride-hydrochloride [ (C5H4CHzCHz-N(H)iPr2)(C5H4SiMe3)TiC1,]+C1-(2). The structure of 2 was determined by a single-crystal X-ray diffraction study. Com-pounds 1 and 2 are precursors for ethylene polymerization catalysts. The reaction of 2 with one equivalent of Na+B[3,5-(CF3)2C&]: afforded the borate [ (C5H4CH2CH2N(H)Pr2)-(C5H4SiMe3)TiC12]+B[ 33-( CF3)2C6H3]: (3). The dimethyl compound (C5H4CH2CH2NiPr2)(C5H&iMe3)TiMe2 (4) was obtained by reaction of 1 with two epuivalents of methyllithium. The diphenoxy complex (C5H4CH2CH2-NiPr2)(C5H4SiMe3)Ti(OPh)2 (5) was prepared analogously with a stoichiometric amount of lithium phenoxide. Compounds 4 and 5 show remarkable activity in the catalytic dehydrocoupling of phenylsilane.

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Section: Resultsmentioning

confidence: 99%

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

et al. 1996

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“…Treatment of dichlorobis(3,5-di- tert -butylpyrazolato)titanium(IV) with tert -butylamine would result in the formation of a tert -butylamide complex along with production of tert -butylammonium chloride. A similar reaction occurs upon treatment of titanocene dichloride with primary amines to afford stable complexes of the formula Cp 2 Ti(NHR)(Cl) . The tert -butylamide complex then eliminates 3,5-di- tert -butylpyrazole to afford the fragment (tBu 2 pz)Ti(NtBu)(Cl), which dimerizes to give 5 .…”

Section: Resultsmentioning

confidence: 95%

Imido Complexes of Titanium Bearing η²-Pyrazolato Ancillary Ligand Sets

1999

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Treatment of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) with Grignard (CH3MgCl, C6H5CH2MgCl) or organolithium (LiCH2Si(CH3)3) reagents (2 equiv) afforded the dialkyl derivatives dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (93%), dibenzylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (43%), and bis(methyltrimethylsilyl)bis(3,5-di-tert-butyl-pyrazolato)titanium(IV) (49%). Analogous methylation of chlorotris(3,5-di-tert-butylpyrazolato)titanium(IV) with CH3MgCl afforded methyltris(3,5-di-tert-butylpyrazolato)titanium(IV) (52%). Attempted alkylation of trichloro(3,5-di-tert-butylpyrazolato)titanium(IV) with CH3MgCl (3 equiv) afforded dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (35%), along with extensive decomposition. This experiment indicates that trimethyl(3,5-di-tert-butylpyrazolato)titanium(IV) is unstable at ambient temperature. The reactivity of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) and dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) toward primary amines was studied. Treatment of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) with excess tert-butylamine afforded tert-butylimido(chloro)(3,5-di-tert-butylpyrazolato)titanium(IV) dimer (10%), chlorotris(3,5-di-tert-butylpyrazolato)titanium(IV) (56%), and tert-butylammonium chloride (85%). Analogous treatment of dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) with tert-butylamine gave the monomeric imido complex tert-butylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) (33%). Addition of pyridine to the reaction between dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) and tert-butylamine or isopropylamine afforded the pyridine adducts tert-butylimidobis(3,5-di-tert-butylpyrazolato)(pyridine)titanium(IV) (80%) and isopropylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) (46%), respectively. Treatment of dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) with 1-amino-4-methylpiperazine led to the hydrazide(1−) complex 1-amido-4-methylpiperazine(methyl)bis(3,5-di-tert-butylpyrazolato)titanium(IV) (64%), which contains both a titanium−methyl bond and a primary hydrazide(1−) ligand. It is proposed that the thermal stability of this compound arises from bidentate coordination of the hydrazide(1−) ligand, which places the reactive nitrogen−hydrogen bond distal to the titanium−methyl bond. The reactivity of tert-butylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) toward acetylenes, nitriles, and ketones is discussed. The X-ray crystal structures of bis(methyltrimethylsilyl)bis(3,5-di-tert-butyl-pyrazolato)titanium(IV), tert-butylimido(chloro)(3,5-di-tert-butylpyrazolato)titanium(IV) dimer, and isopropylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) were determined.

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Titanium Compounds, Organic

Putzig

Pesco

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Organic titanium compounds are materials having a covalent bond between titanium and another atom that is also bonded to a carbon‐based group. Titanium tetrachloride, the basic raw material from which organic titanate compounds are made, is readily converted to tetraisopropyl titanate, TYZOR TPT, by the Nelles process. This ester can be converted by alkoxy exchange (transesterification) to a wide variety of tetraalkyl titanates, which in turn react with other ligands and chelating agents to give complexes having properties significantly different from the starting materials. This article covers all aspects of the organic titanium compound, from properties, reactions, and synthesis, to uses and health and safety factors.

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The Preparation of Ammonolysis and Aminolysis Products of Bis(cyclopentadienyl)titanium Dichloride

Cited by 14 publications

References 5 publications

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

Imido Complexes of Titanium Bearing η²-Pyrazolato Ancillary Ligand Sets

Titanium Compounds, Organic

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The Preparation of Ammonolysis and Aminolysis Products of Bis(cyclopentadienyl)titanium Dichloride

Cited by 14 publications

References 5 publications

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

Titanium and Zirconium Bent-Sandwich Complexes with the New [2-(Diisopropylamino)ethyl]cyclopentadienyl Ligand: Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane

Imido Complexes of Titanium Bearing η2-Pyrazolato Ancillary Ligand Sets

Titanium Compounds, Organic

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Imido Complexes of Titanium Bearing η²-Pyrazolato Ancillary Ligand Sets